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Patented Aug. 8, 1939 UNITED STATES PATENT OFFIE DIAZOAMINO COMPOUNDSSOLUBLE IN WA- TEE AND PROCESS OF PREPARING THEM Herbert Kracker andRichard Schmid, Frankforton-the-Main-Hochst, Germany, assignors toGeneral Aniline Works, Inc., New York, N. Y., a. corporation of DelawareN0 Drawing. Application October 14, 1936, Se-

rial No. 105,630. In Germany October 17,

8 Claims. (01. 260-140) boxylic acid, sulfonic acid or hydroxyl groups,or

wherein R and R jointly stand for the radical of a heterocyclic ringsystem in which the nitrogen is the hetero-atom and which containsgroups lending solubility in water, and which are obtainable fromdiazotized amines, which in their nondiazotized form are capable ofbeing coupled with diazo-compounds to form amino-azo-bodies, andnitrogen bases soluble in water, may be combined with diazo-compoundsnot containing any group lending solubility in water in a smoothreaction and with a very good yield with formation of water-solublediazoamino-compounds of aminoazo-bodies. The compounds obtained may beregarded as corresponding with the following general formula:

RN=N -N=N-NR wherein R, R and B" have the meaning indicated above and Rstands for an aromatic or a heterocyclic radical which does not containany solubilizing group.

Thus, for instance, the diazoamino-compound fromaminohydroquinone-dimethyl ether and sarcosine may be combined withdiazotized paranitraniline to form a diazoamino-compound of thefollowing constitution:

CH OOHa 3 By using, instead of aminohydroquinone-dimethyl ether, otheramines capable of being'coupled, for instance, l-naphthylamine,l-amino-Z-methoxy- E-methylbenzene, l-amino-3-methoxy4-methyl benzeneand the like, instead of sarcosine any other nitrogen bases which areknown as stabilizers for diazoamino-compounds and, instead ofdiazotized' para-nitraniline, other diazo-compounds, thediazo-amino-compo-unds of the corresponding aminoazo-bodies are formedin the same manner.

It has not hitherto been known, and must be regarded as surprising thatthe diaZo-group presv ent in the form of the 'diazoamino group allows,in the aromatic radical to which it is bound, another coupling with adiaZo-compound to form an azobody.

The diazoamino-compounds of aminoazo-bodies thus obtained are valuableintermediates for the manufacture of dyestuffs.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto: 1

(1) 30.6 grams of 1-amino-2.5-dimethoxybenzene are diazotiz ed in theusual manner at 3 C.-5 C. with cc. of hydrochloric acid of 20 B. and cc.of .2N-sodium nitrite solution. The diazo-solution obtained is caused torun slowly at 0 C. into grams of a sarcosine solution of 15 per cent.strength to which there has been added a solution of 50 grams ofcalcined sodium carbonate in water. The formation of the diazoamino-bodyis finished after some hours. By salting out with sodium chlorideamounting to 15 per cent. of the volume of the solution, thediazoamino-compound is completely precipitated in the form of areddish-brown crystalline mass and is then isolated.

80 grams of the diazoamino-compound obtained are dissolved in 500 cc. ofwater at 25 C. we clear solution, and a solution at 20 C. of 80 grams ofcalcined sodium carbonate in water is then added. Into this solutionthere is run slowly a diazo-solution prepared in the usual manner from41.4 grams of para-nitraniline. The a'zodyestuff is rapidly formed and aclear solution having an alkaline reaction towards Brilliant- Yellow isobtained. After stirring for some hours, the dyestuif is completelyprecipitated by cautiously neutralizing the solution with dilutehydrochloric acid until it shows only a feebly alkaline reaction towardsBrilliant-Yellow and salting out. After filtering by suction and dryingat about 60 C. the compound is obtained in the form of a reddish-brownpowder with a yield of 85 per cent. of the theoretical. It has thefollowing formula:

OCH;

moo

(2) 137 grams of 1 amino 3 methoxy 4 methylbenzene are diazotized in theusual manner. The diazo-solution is slowly run at 0 C. into a solutionwhich has been prepared as follows: 149 grams of methyltaurine aredissolved in 500 cc. of ice water; a solution of 280 grams of calcinedsodium carbonate in 1000 cc. of water is then added. Thediazoamino-compound is completely formed after some hours. It separatesin the form of a yellowish-brown paste; after filtering with suction itis dried at 60 C.-'70 C.

150 grams of the diazoamino-compound thus obtained are mixed, whilestirring, with 1000 cc. of water and a small quantity of ice. In order.to obtain a good dispersion, 15 cc. of a solution of 30 per cent.strength of the reaction product of 20 mols. of ethylene oxide upon 1mol. of 0ctodecyl alcohol are added. At 3 C.-5 C. there is slowly runinto the suspension of the diazoamino body a diazo-solution which isprepared in the usual manner from 86 grams of l-amino-2-chloro-4-nitrobenzene and, simultaneously, a

suspension of 200 grams of sodium bicarbonate in 600 cc. of water isadded in small portions so that the whole shows always an alkalinereaction to Brilliant-Yellow. The addition of the whole quantity ofbicarbonate at the same time must be avoided in order to preventdecomposition of the diazo-solution before coupling has occurred. Theformation of the azo-dyestufi sets in at once with production of areddish-brown coloration and is finished the next day. The reaction mustbe feebly but distinctly alkaline to Brilliant-Yellow. The dyestufl isprecipitated for the most part in the form of reddish-brown crystals. Byadding sodium chloride amounting to 5 per cent. of the volume of theliquid, the dyestuff is completely precipitated. After filtering withsuction and drying at about 60 C. the compound is obtained in the formof a dark red-brown powder with a nearly theoretical yield.

(3) 40 grams of the brown diazoamino-compound, which is obtainable bycombining in the usual manner diazotized l-naphthylamine with1--methylaminobenzene-2-carboiwlic acid4-sul ionic acid, are dissolvedin 500 cc. of water at ordinary temperature, cooled to 5 C. and 30 gramsof calcined sodium carbonate dissolved in water are added. Into thissolution there is run slowly a diazo-solution prepared in the usualmanner from 13.7 grams of 1-amino-2-ethoxybenzene. The azo-dyestuff isformed slowly and is finished the next day. The reaction must bedistinctly alkaline to Brilliant-Yellow. By cautiously neutralizinguntil a feebly alkaline reaction to Brilliant-Yellow is obtained and-bysalting out, the dyestuff is completely precipitated. After drying, thediazoamino-compound is obtained in the form of a black-brownish powderwith a yield of 92 per cent. of the theoretical.

(4) 41.2 grams of the feebly yellowish-brown crystallinediazoamino-compound, which is obtainable in the usual manner fromdiazotized 1-amino-2-methoxy-5-methylbenzene and sarcosine, aredissolved in 400 cc. of water. 30 grams of calcined sodium carbonate arethen added in the form of a solution of l5-20 per cent. strength and adiazo-solution prepared in the usual manner from 15.2 grams of l-amino-2-nit-ro-4-methylbenzene is then slowly run in. The formation of theazo-dyestuff sets in slowly and is finished the next day. Theprecipitated dyestuff is filtered with suction and dried, at about 60 C.It is a red-brown powder and is obtained with a yield of per cent. ofthe theoretical.

The following table indicates a number of other diazoamino-compoundsobtainable according to the present invention:

Coupled with the diazoamino-compound irom- Properties ol thedialoamino-compound of No. Diazo compound from the pminoazo bodyD1azot1zed Andobtained 1 l amino 2.6 dichloro 4nitrol-amino-2.5-dimethoxy-benzene Mcthyltaurine Black-brown crystallinebenzene. powder. 2 1 amino 2 methyl 6 chloro- .do Praline Dark browncrystalline benzene. powder. 3 lamino 2.6 d1chloro-4 -n1trodo 1methylamino 2 hydroxypro- Dark brown powder.

benzene. pane-3-sulfonic acid. l-amino-i-chloronaphthalene do 1ethylamino 2 hydroxypro- Black-brown powder.

l-am in o-ii-nitro-benzene 1 amino 3 methoxy 4 chlopane-3-sulron1c acid.

1 amino benzene 2 carboxyiic Dark brown crystalline robenzene.acid-5-sulfam1de. powder. l-amino-2.5-d1chlorobenzene doHydroxyethyl-amino-acetic acid. Do. 1 -am1no -2-cbloro- 5 trifiuoro- 1amino 3 methoxy 5 bro- Pi ecolinic acid Do.

methyl-benzene. mobenzene. l amino 2 nitro 4 -methoxydo 1 methylamino-benzenc 2 car- Do.

benzene. boxylic acid-dsuli'onic acid. 1-ammo-2-methyl-4-mtrobenzencl-amino-Zi-rnethoxy- 4-metl1yl- Cyanamide Dark red-brown crystalbenzene. line powder. 1-ammo-2.4-dichloro-6-mtrobendoPiperidine-alpha-sulfonic acid... Do.

zene. 4 amino 3 trifiuoromethylben- .do Butylamino-acetic acid Do.

zene. l-am in o'2- nitro- 4- trifluorodo l-aminobenzene-Z-carboxylicacid- Do.

mcthylbcnzene. 5-sulfonic acid. 1 -amino-2-chloro-4-mtrobenzene. .do 1methyl amino 2 hydroxypro- Dark-brown powder.

2-amino-l-nitronaphthalene 1-amino4-n1trobcnzene Do. Dark-rcd-browncrystal line powder.

N o. Diazo-compound from- Ooupled with the diazoamino-compound from-Properties of the diazoamino compound of the aminoazo body Diazotized-And obtained 1-amino-2-methy1-4-chlorobcndo Piperazino-acetic acid Do.

zene. l-aminoi-methoxy-benzene l-naphthylemine Hydroxyethyl-taurineBrown-black powder. 1-am1no-2-n1trobenzenel-amino-2-methoxy-naphthalene. Pyrrolidine-aJpha-sulfonic acid.-. Do.1-amlno-2-Inethoxy5-nitrobendo 1-aminobenzene-2-carboxylic acid- Do.

zene. ii-sulfonic acid.1-am1no-2-methoxy-5-chlorobenl-amino-5-methoxynaphthalenePiperidine-beta-sulfonic acid Do.

Z9116. 1 amino -2-methy1-3 chlorodo Methyltaurine Do.

benzene. l-amino-3-chlorobenzene 1-an1ino-2-1nethylnaphthalenc; Proline.Do. 23..- 1 ammo 5 trifiuoromethyll amino 2 methoxy 5Hydroxyethyl-taurine Red-brown powder.

phcnyl-Z-ethylsull'one. Inethylbenzene. 24. 1 amino 2 methyl 4 nitro 1-amino -2-methoxy-5-methyl- 1 Inethylamino benzene 2 car- Dark brownpowder.

benzene. benzene. boxylic acid-4-su1fonic acid. 25..." 1 amino 2 chloro4 nitrol amino-2-metl1yl-5-methoxy- Butylamino-acetic acid Do.

benzene. benzene. 26. 1 amino 2 inethoxy 5 nitrodo Methylglucamine Do.

benzene. 27 1 amino 3.5 -bistrifluorol-amino-3-methoxybenzeneMethyltaurine Do.

methylbenzene. 28 1 ang na 2 methoxy- 4 chlo- ..doPiperidine-alpha-sulionlc acid... Red-brown powder.

roenzene. 29 1 amino 3.5 bis trifluoro- 1-amino-2.5-diethoxy-benzene 1aminobenzene 2 carboxylic Do.

methylbenzcne. acid-4-sulion1c acld amide. 30 l-amino-B-chlorobenzene doSarcosine.. Do. 31 1 amino 2 nitro 4 methyl- 1 amino 3 methoxy 6 chlo-Ethylene-diamine-di-acetic acid. Brown powder.

benzene. robenzene. 32 1-amino-2-methoxybenzene-5- ,do Methyltaurine Do.sulfonic acid-diethylamide. 2D 33 l-gmino-3-methy1-4.6-dichl0r0-l-amino-3.5-dimethoxybenzene Piperidlne-alpha-carboxylic acid Do.

enzene. 34"... l-amino-2 -trifluoromethyl-5- do Cyanamide Yellow-brownpowder.

chlorobenzene. 35 l-amino-2-chlorobenzene1-arnino-3-ethoxy-4-1nethylben- Butylamino-acetlc acid Red-brown powder.

zenc. 36.- l-amino-3-benzoy1amino-4.6-dido .r Piperidine-beta-carboxylicaeid Dark brown powder. 30

methylbenzene. 37. 2.4-dichloroaniline 1-an1ino-4-methy1-2.fi-dimethoxy-Phenylglycme-S-sulfonic acid Do.

benzene. aimde. 38 l-fiminO-2-IHethy1-4.5-dichl0rodol-aminobenzene-2-carboxylic acid- Do.

benzene. 4-sulfonic acid. 39 l-amino-2-methoxy-5-ch1oroben-1-amino-4-ch1oro-2.5-dimethoxy- Hydroxyethyl-taurine Do.

zene. benzene. 40. 2-amino-diphenylsulfone "do5-amino-iurane-2-carboxylie acid Do. 30 41..." l-aminolbenzoylamino-2--1-amino-4-brom0 Hydroxyethylainino-acetic acid Black-brown powder.

methoxy5-methylbenzene. benzene. 42 Lamino-Ei-nitrobenzene do 1methylamlno 2 hydroxypro- Do.

pane-3-su1fonic acid. 4 43. l-amino-2-nitro-4-methoxy- 1 amino 2.4.5trimethoxy- Cyclohexyl-amino-acetic acid Dark brown powder.

benzene. benzene. 44"." l amino 2 chloro 4 nitro- ,do 1 methylaminohexahydroben- Do.

benzene. zene-3-sulionic acid. 45. 1 1amino 2 methoxy 4 nitro- 2 amino 4-methoxy -naphtha- Oxethylamino-acetic acid Brown-black powder.

enzene. lene. 46. 1 amino 4 benzoylamino 2 ,do Piperidine-alpha-sulfonicacid... Do.

.ch1oro-5-methoxybenzene. 47 1 amino 2 methoxy 4 chlo-1-aInino-3-ethoxy-benzene Cyclohexyl-ammoacetm acid Brown powder.

ro-benzene. 48.. l-amino -4-benzoylamino-2.5- do Piperazino-acetic acidDark brown powder.

dimethoxybenzene. 9--." 1-an1ino-4-nitrobenzene 1 amino 4 benzoyl amino1 -methylam1no 2-hydroxy -pro- Black-brown powder.

2.5-dimethoxy-benzene. pane-3-sulfonie acid. 50... 2.5-dich1oro-ani1inedo l-fainmo (1i1aphtl1alene-2.4-disul- Do.

01110 3.01 51. 1 amino 4 chloro 2 nitro 1 -amino -4 -benzoylamino -2.5-Beta gamma d i hydroxypro- Do.

benzene. diethoxy-benzene. pylammo acetic acid. 52l-aminO-ZA-dinitro-benzane dc Hydroxy ethylamino ethane Do.

sulfonic acid.

We claim: selected from the group consisting of carboxylic 1. Theprocess which comprises combining with Field, sulfonic acid and hydroxylgroups, or wheredjazo compounds not containing groups impartin R and RJointly stand for the radical Of a 55 ing solubility in water selectedfrom the group heterocycllc llng System in Whlch mtlogen consisting ofcarboxylic acid, sulfonic acid and 15 h j P and 7111011 Contams groupshydroxyl groups the diazoamino-compounds corlendlng q llefl ty I Waterselected from the responding with the following general formula: up nsstm f carb xy a Sulfomc a I, T and hydroxyl groups. R 2. The processwhich comprises combining with diazotized 1amino-2-chloro-4-nitrobenzenethe wherein stand for h i 1 f an in diazoam1no-compound obtainable fromdiazotized S t 8 ad ca 0 am e 1-amino-3-methoxy-4-methylbenzene and 1-capable of being coupled selected from the group consisting of radicalsof the benzene and naphmethylammo'zfhydroxypropane'3'sulfomc acldthalene series not containing groups imparting and corresponding withthe following formula: solubility in water selected from the groupconsisting of carboxylic acid, sulfonic acid and i hydroxyl groups, Rstands for a member of the group consisting of hydrogen, alkyl, hydroxy-H3C- NN N CH OH CHS0N alkyl, hydroaryl and a radical of the benzene OH;H series, R for a member of the group consisting of aliphatic,hydroaromatic and heterocyclic radicals The D Whlch COmDPISES CombinmgWllih andradicals of the benzene and naphthalene series d Dt Z d-amino-2. -d1ch1or0-4-nitrobenzene containing groups impartingsolubility in water the cliazoamino-compound obtainable from diazotizedl-amino-2.5-dimethoxybenzene and 1-methylamino-2-hydroxypropane-3-sulfonic acid and corresponding with thefollowing formula:

OCH;

N N-N-OSOaNa l COONa 5. The diazoamino-compounds soluble in watercorresponding with the following general formula:

B-N=N-RN=NNR wherein R" stands for the radical of an amine capable ofbeing coupled selected from the group consisting of radicals of thebenzene and naphthalene series not containing groups impartingsolubility in water selected from the group consisting of carboxylicacid, sulfonic acid and hydroxyl groups, R stands for a member of thegroup consisting of hydrogen, alkyl, hydroxyalkyl, hydroaryl and aradical of the benzene series, R for a member of the group consisting ofaliphatic, .hydroaromatic and heterocyclic radicals and :radicals of thebenzene and naphthalene series containing groups imparting solubility inwater selected from the group consisting of carboxylic acid, sulfonicacid and hydroxyl groups, or wherein R and R jointly stand for theradical of a heterocyclic ring system in which the nitrogen is thehetero-atom and which contains groups lending solubility in waterselected from the group consisting of carboxylic acid, sulfonic acid andbeing a dark-brown powder soluble in water.

7. The diazoamino-compound of the following formula:

OCH

c1 3 O2N N=N N=N-1 II-cH2-cr1-cms olNa OH; on

01 com being a dark-brown powder soluble in water.

8. The diazoamino-compound of the following being a black-brownishpowder soluble in water.

HERBERT KRACKER. RICHARD SCI-IMID.

